Metal-Organic Frameworks as Porous Proppants

Patent metadata

Field	Value
Publication number	US-2017145299-A1
Application number	US-201415319331-A
Country	US
Kind code	A1
Filing date	Jul 15, 2014
Priority date	Jul 15, 2014
Publication date	May 25, 2017
Grant date	—

Abstract

The invention provides metal-organic frame-works (MOFs) and its compositions for use as proppants in a method of treating subterranean formations.

First claim

We claim:

1 . A method of treating a subterranean formation, the method comprising contacting the formation with a fluid composition comprising a metal-organic framework comprised of at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion.

2 . The method according to claim 1 , wherein the metal ion is selected from available ions of base elements in the group consisting of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Gd, Eu, Tb, and combinations thereof.

3 . The method according to claim 2 , wherein the base element is selected from the group consisting of Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, and combinations thereof.

4 . The method according to claim 1 , wherein the ligand contains at least one functional group selected from the group consisting of a carboxylate, a phosphonate, an amine, an azide, a cyanide, a squaryl, an heteroatom, and combinations thereof.

5 . The method according to claim 4 , wherein the ligand is selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, imidazole, ions, salts and combinations thereof.

6 . The method according to claim 5 , wherein the ligand is selected from the group consisting of formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic acid, (E)-butenedioic acid, benzene-1,4-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid, 2-bromo-1,4-benzenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, biphenyl-3,3′,5,5′-tetracarboxylic acid, biphenyl-3,4′,5-tricarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa-2,4-dienedioic acid, 1,4-naphthalenedicarboxylic acid, pyrene-2,7-dicarboxylic acid, 4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid, aspartic acid, glutamic acid, adenine, 4,4′-bypiridine, pyrimidine, pyrazine, pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole, 1H-benzimidazole, 2-methyl-1H-imidazole, ions, salts, and combinations thereof.

7 . The method according to claim 1 , wherein the metal ion is an ion of Zn and the ligand is benzene-1,4-dicarboxylic acid.

8 . The method according to claim 1 , wherein the metal ion is an ion of Cu and the ligand is benzene-1,3,5-tricarboxylic acid.

9 . The method according to claim 1 , wherein the metal-organic framework has a dry density of about 0.2 g/cm 3 to about 0.8 g/cm 3 .

10 . The method according to claim 1 , wherein the metal-organic framework has a pore size from about 0.2 nm to about 30 nm.

11 . The method according to claim 1 , wherein the metal-organic framework is present in the form of a shaped body having a shortest dimension of at least about 0.2 mm and a longest dimension of about 3 mm.

12 . The method according to claim 11 , wherein the shaped body is selected from the group consisting of a spherical body, a cylindrical body, a disk-shaped pellet, and combinations thereof.

13 . The method according to claim 1 , wherein the composition further comprises a binder.

14 . The method according to claim 13 , wherein the binder is selected from the group consisting of hydrated aluminum-containing binders, titanium dioxide, hydrated titanium dioxide, clay minerals, alkoxysilanes, amphiphilic substances, graphite, and combinations thereof.

15 . The method according to claim 1 , wherein the contacting comprises placing the composition in at least one of a fracture and flowpath in the subterranean formation.

16 . The method according to claim 15 , wherein the fracture is present in the subterranean formation at the time when the composition is contacted with the subterranean formation.

17 . The method according to claim 16 , wherein the method further comprises forming the fracture or flowpath.

18 . The method according to claim 1 , wherein the contacting comprises gravel packing.

19 . The method according to claim 1 , further comprising fracturing the subterranean formation to form at least one fracture in the subterranean formation.

20 . The method according to claim 1 , wherein the composition further comprises a carrier fluid.

21 . The method according to claim 1 , wherein the metal-organic framework is present in an amount of about 0.01 wt % to about 30 wt % based upon the total weight of the composition.

22 . The method according to claim 21 , wherein the metal-organic framework is present in an amount of about 0.1 wt % to about 10 wt %.

23 . The method according to claim 1 , further comprising combining the composition with an aqueous or oil-based fluid comprising a fracturing fluid, spotting fluid, clean-up fluid, completion fluid, remedial treatment fluid, abandonment fluid, pill, cementing fluid, packer fluid, or a combination thereof.

24 . A system for performing the method of claim 1 , the system comprising:
a tubular disposed in the subterranean formation; and a pump configured to pump the composition in the subterranean formation through the tubular.

25 . A system comprising:
a fluid composition comprising a metal-organic framework comprised of at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion subterranean formation comprising the composition therein.

26 . The system according to claim 25 , further comprising:
a tubular disposed in the subterranean formation; a pump configured to pump the composition in the subterranean formation through the tubular.

Assignees

• Halliburton Energy Services Inc

Inventors

• Schultheiss Nathan Carl
• Lu Zheng
• Oliveira Humberto Almeida
• Benoit Denise Nicole
• Palla-Venkata Chandra Sekhar

Classifications

• C09K8/536

  characterised by their form or by the form of their components, e.g. encapsulated material · CPC title

• E21B43/04

  Gravelling of wells · CPC title

• C09K8/80 Primary

  Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open · CPC title

• C09K8/03 Primary

  Specific additives for general use in well-drilling compositions · CPC title

• E21B43/267 Primary

  reinforcing fractures by propping · CPC title